Molecularly engineered brush-like graft copolymers and compositions and methods thereof

Abstract

The subject matter described herein is directed to molecularly engineered brush-like graft copolymer elastomers and applications thereof. The developed formulation platform is based on the synthesis of brush-like graft copolymer networks with engineered macromolecular architecture composed of brush-like polymers, such as combs and bottlebrush polymers, and block copolymers composed of combinations of brush and linear blocks, with capability of bearing desired chemical functionalities, for example, brush side-chains, chain-ends, and/or brush backbone.

1 . A hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single-molecule composition thereof, wherein the hybrid brush-like graft copolymer has an: 
       
         
           
           
               
               
           
         
         architecture, the hybrid brush-like graft copolymer comprising:
 a B block that is a residue of a first macromonomer; 
 an A block that is a residue of a second macromonomer that is different than the first macromonomer; 
 a g spacer; and, 
 a backbone which is a polymer or copolymer;
 wherein the A block and the B block are selected to programmably predetermine the viscoelastic properties of the copolymer. 
 
 
       
     
     
         2 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the hybrid brush-like graft copolymer self-assembles due to microphase separation. 
     
     
         3 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 2 , wherein the microphase separation forms physically distinct domains of linear polymer blocks dispersed within a matrix of the brush-like polymer blocks. 
     
     
         4 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the B block controls mechanical properties, and the A block controls phase separation properties. 
     
     
         5 - 7 . (canceled) 
     
     
         8 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the viscoelastic properties are defined as one or more architectural parameters selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         9 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the adhesion property of the hybrid brush-like graft copolymer, single molecule composition is programmably determined through one of more of n sc , n g , and n x . 
     
     
         10 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the firmness and cohesive strength of the hybrid brush-like graft copolymer, single molecule composition is programmably determined through one of more of n bb , n A , and ϕ A . 
     
     
         11 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the backbone is a polymer of acrylate, methacrylate, styrene or copolymers thereof. 
     
     
         12 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the g spacer is a residue of acrylate, methacrylate, styrene or glycol. 
     
     
         13 - 14 . (canceled) 
     
     
         15 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the g spacer is an acrylate/methacrylate copolymer. 
     
     
         16 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the first macromonomer is selected from the group consisting of residues of polyacrylates, methacrylates, polyolefins, polysiloxanes, polyesters, polyethers, polyureas, polyurethanes, polystyrene, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl chloride, polyethylene glycol, polylactides, polyglycolides, poly(lactide-co-glycolide), polyacrylonitriles, polylactones, polycaprolactams, polyoxazolines, poly(propylene fumarate), polynorbornenes, and polycarbonates and copolymers thereof. 
     
     
         17 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 16 , wherein the first macromonomer is functionalized with aldehyde, isocyanate, amine, diene, dienophile, epoxide, cyanoacrylate, thiol, catechol, oligonucleotide, hydrogen bond donor/acceptor group, alkyne, alkoxy, azide, vinyl, acrylate, methacrylate, carboxylic acid, alkoxy, oxime, acetoxy, amide, urea, guaiacol, furan or hydroxyl moieties. 
     
     
         18 - 20 . (canceled) 
     
     
         21 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of any one of  claim 1 , wherein the second macromonomer is selected from the group consisting of residues of, polyacrylates, methacrylates, polyolefins, polysiloxanes, polyesters, polyethers, polyureas, polyurethanes, polystyrene, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl chloride, polyethylene glycol, polylactides, polyglycolides, polylactides, poly(lactide-co-glycolide), polyacrylonitriles, polylactones, polylactams such as polycaprolactams, polyoxazolines, poly(propylene fumarate), polynorbornenes, and polycarbonates including any potential copolymers of the aforementioned chemistries; or is selected from the group consisting of vinyl polymers (e.g., polystyrene, poly(vinyl acetate), poly(acrylo nitrile), and poly(vinyl alcohol)), alkyl acrylate derivatives, alkyl methacrylate derivatives (e.g., poly(methyl methacrylate) and poly(benzyl methacrylate)), ether acrylate derivatives, ether methacrylate derivatives (e.g., poly(oligo (ethylene glycol) monomethyl ether methacrylate), olefin acrylate derivatives, olefin methacrylate derivatives, and olefin norbomene derivatives, and copolymers thereof. 
     
     
         22 . (canceled) 
     
     
         23 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the first macromonomer is selected from the group consisting of residues of polyacrylates, polyolefins and polysiloxanes. 
     
     
         24 . (canceled) 
     
     
         25 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of any one of  claim 1 , wherein the second macromonomer is selected from the group consisting of residues of polystyrene, PMMA, PLA and PVC. 
     
     
         26 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of any one of  claim 1 , wherein the hybrid brush-like graft copolymer is selected from the group consisting of poly[MMA-g-(PDMS/PMMA)], poly[MMA-g-(PnBA/PMMA)], poly[MMA-g-(PIB/PMMA)], poly[MMA-g-(PDMS/PS)], poly[MMA-g-(PnBA/PS)], poly[MMA-g-(PIB/PS)], poly[nBA-ran-MMA-g-(PDMS/PS)], poly[nBA-ran-MMA-g-(PnBA/PS)], poly[nBA-ran-MMA-g-(PIB/PS)], poly[nBA-ran-MMA-g-(PDMS/PMMA)], poly[nBA-ran-MMA-g-(PnBA/PMMA)] poly[nBA-ran-MMA-g-(PIB/PMMA)], poly[MMA-g-(PDMS/PLA)], poly[MMA-g-(PnBA/PLA)], poly[MMA-g-(PIB/PLA)], poly[MMA-g-(PDMS/PLGA)], poly[MMA-g-(PnBA/PLGA)], poly[MMA-g-(PIB/PLGA)], poly[MMA-g-(PDMS/PCL)], poly[MMA-g-(PnBA/PCL)], and poly[MMA-g-(PIB/PCL)]. 
     
     
         27 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of any one of  claim 1 , wherein the composition has been formed as a pressure sensitive adhesive; or, wherein the composition has been formed for pressure sensitive adhesive formulations. 
     
     
         28 - 29 . (canceled) 
     
     
         30 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the composition is in the form of a three-dimensional shape that has been molded. 
     
     
         31 . (canceled) 
     
     
         32 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of  claim 1 , wherein the composition is essentially free of solvents. 
     
     
         33 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of any one of  claim 1 , wherein the composition is essentially non-leachable. 
     
     
         34 . The hybrid brush-like graft copolymer, or hybrid brush-like graft copolymer, single molecule composition thereof of any one of  claim 1 , wherein the composition does not comprise additional additive components. 
     
     
         35 - 38 . (canceled) 
     
     
         39 . A method of programmably predetermining the viscoelastic properties of a hybrid brush-like graft copolymer, the method comprising:
 i. preparing a mixture comprising a B block first macromonomer and an A block second macromonomer, wherein the first and second macromonomer are different from each other;   
       and,
 ii. subjecting the mixture to polymerization selected from the group consisting of free radical polymerization (FRP), atom transfer radical polymerization (ATRP), SARA ATRP, anionic polymerization, and reversible addition-fragmentation chain-transfer polymerization (RAFT), ring opening polymerization, ring opening metathesis polymerization, metallocene polymerization, and coordination polymerization, 
 wherein, a hybrid brush-like copolymer having an 
 
       
         
           
           
               
               
           
         
          architecture and programmably predetermined viscoelastic properties is prepared. 
       
     
     
         40 - 51 . (canceled)